title: Synthesis and structural characterization of bis and tris(2-mercapto-1-methylbenzimidazolyl)hydroborato complexes: benzannulation promotes κ³-coordination.
abstract: The benzannulated bis and tris(mercaptoimidazolyl)borohydride compounds, [BmMeBenz]Na and [TmMeBenz]Na, have been synthesized via the reactions of NaBH4 with two and three equivalents of 1-methyl-1,3-dihydro-2H-benzimidazole-2-thione, respectively. X-ray diffraction studies on the THF adducts, {μ-[BmMeBenz]Na(THF)₂}₂ and {[TmMeBenz]Na}₂(μ-THF)₃, indicate that both compounds are dinuclear but differ according to the nature of the bridging ligand. Specifically, {μ-[BmMeBenz]Na(THF)₂}₂ possesses bridging [BmMeBenz] ligands and terminal THF ligands, while {[TmMeBenz]Na}₂(μ-THF)₃ possesses terminal [TmMeBenz] ligands and bridging THF ligands. The tris(mercaptoimidazolyl)borohydride ligand of {[TmMeBenz]Na}₂(μ-THF)₃ coordinates in a κ³-manner, which is in marked contrast to the κ²-, κ¹- and κ⁰-modes that have been reported for various [TmMe]Na derivatives. Density functional theory (DFT) geometry optimization calculations of the anions [TmMeBenz]⁻ and [TmMe]⁻ in the gas phase indicate that the conformation required for κ³-S₃ coordination, i.e. one in which the three sulfur donors point away from the B-H group, is relatively more stable for [TmMeBenz]⁻ than for [TmMe]⁻, and thus provides a rationalization for the observation that benzannulation enables κ³-coordination of tris(mercaptoimidazolyl)borohydride ligand in {[TmMeBenz]Na}₂(μ-THF)₃. Furthermore, comparison of the molecular structure and IR spectroscopic properties of [TmMeBenz]Re(CO)₃ with those of [TmMe]Re(CO)₃ indicates that benzannulation reduces the electron donating properties of the ligand, but has little effect on its steric properties. {μ-[BmMeBenz]Na(THF)₂}₂ and {[TmMeBenz]Na}₂(μ-THF)₃ react with [Me₃PCuCl]₄ to give [BmMeBenz]CuPMe₃ and [TmMeBenz]CuPMe₃, the first pair of structurally related bis and tris(mercaptoimidazolyl)hydroborato copper(I) compounds.
authors.affiliation: Department of Chemistry, Columbia University, New York, NY 10027, USA.
authors.forename: Ahmed
authors.initials: A
authors.lastname: Al-Harbi
authors.forename: Yi
authors.initials: Y
authors.lastname: Rong
authors.forename: Gerard
authors.initials: G
authors.lastname: Parkin
mesh_terms: D001896:Boron Compounds / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007093:Imidazoles / Q000737:chemistry*; D008024:Ligands; D008968:Molecular Conformation
chemical_list: D001896:Boron Compounds; D056831:Coordination Complexes; D007093:Imidazoles; D008024:Ligands; C029899:imidazole